Compositions comprising 2,3,3,3-tetrafluoropropene, 2-chloro-2,3,3,3-tetrafluoropropanol, 2-chloro-2,3,3,3-tetrafluoro-propyl acetate or zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride

ABSTRACT

Compositions comprising CF3CClFCH2OH, CF3CClFCH2OZnCl, and CF3CClFCH2OC(═O)CH3 are useful in processes to make HFO-1234yf. Compositions comprising HFO-1234yf may comprise at least one additional compound selected from the group consisting of CFC-114a (2-dichloro-1,1,1,2-tetrafluoroethane, CCl2FCF3), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF3CHFCl), HCFC-143a (1,1,1-trifluoroethane, CF3CH3), CFO-1113 (2-chloro-1,1,2-trifluoroethene, CClF═CF2), HFO-1123 (1,1,2-trifluoroethene, CHF═CF2), HFO-1132a (1,1-difluoroethene, CH2═CF2), TFE (tetrafluoroethene, CF2═CF2), HCFO-1122 (2-chloro-1,1-difluoroethene, CHCl═CF2), 3,4,4,4-tetrafluoro-2-butanone (CH3C(═O)CHFCF3), acetyl fluoride (CH3C(═O)F), 2-chloro-2,3,3,3-tetrafluoropropanol (CF3CClFCH2OH), 2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF3CClFCH2OC(═O)CH3), Zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF3CClFCH2OZnCl2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate (CF3CFClCH2OCH2OC(═O)CH3), 1,3-bistrifluoromethyl-1,3-difluorocyclobutane (C6H4F8), 2,3,3,3-tetrafluoropropyl acetate (CF3CHFCH2OC(═O)CH3), dimethylformamide (DMF, HCON(CH3)2), pyridine (C5H5N), ethyl acetate, (CHClFCF3), acetic acid (CH3C(═O)OH), diethyl ether (CH3CH2OCH2CH3), acetic anhydride (CH3C(═O)OC(═O)CH3), methyl acetate (CH3C(═O)OCH3), dimethylacetamide (CH3C(═O)N(CH3)2), methanol (CH3OH), ethanol CH3CH2OH), methyl formate (HC(═O)OCH3), pyrazine, pyrimidine, N-methylpyrrolidine, N-methylpiperidine, hexamethylphosphoramide, tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidinone, dimethyl sulfoxide, acetonitrile, benzonitrile, and mixtures thereof. Compositions comprising HFO-1234yf are useful, among other uses, as heat transfer compositions for use in refrigeration, air-conditioning and heat pump systems.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit of U.S. ProvisionalApplication 61/104,334, filed Oct. 10, 2008.

BACKGROUND

1. Field of the Disclosure

The present disclosure relates to the field of compositions which may beuseful as heat transfer compositions, aerosol propellants, foamingagents, blowing agents, solvents, cleaning agents, carrier fluids,displacement drying agents, buffing abrasion agents, polymerizationmedia, expansion agents for polyolefins and polyurethane, gaseousdielectrics, extinguishing agents, and fire suppression agents, all ofwhich may be in liquid or gaseous form. In particular, the presentdisclosure relates to compositions that may be useful as heat transfercompositions, such as 2,3,3,3-tetrafluoropropene (HFO-1234yf, or1234yf). Additionally, the present disclosure relates to compositionscomprising 2-chloro-2,3,3,3-tetrafluoropropanol,2-chloro-2,3,3,3-tetrafluoropropyl acetate or zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride.

These additional compositions are useful in processes to makeHFO-1234yf.

2. Description of Related Art

New environmental regulations have led to the need for new compositionsfor use in refrigeration, air-conditioning and heat pump apparatus. Lowglobal warming potential compounds are of particular interest.

SUMMARY OF THE INVENTION

Applicants have found that in preparing such new low global warmingpotential compounds, such as HFO-1234yf, that certain additionalcompounds are present in small amounts.

Therefore, in accordance with the present invention, in one embodimentthere is provided a composition comprising HFO-1234yf and at least oneadditional compound selected from the group consisting of CFC-114a(2-dichloro-1,1,1,2-tetrafluoroethane, CCl₂FCF₃), HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHFCl), HFC-143a(1,1,1-trifluoroethane, CF₃CH₃), CFO-1113(2-chloro-1,1,2-trifluoroethene, CClF═CF₂), HFO-1123(1,1,2-trifluoroethene, CHF═CF₂), HFO-1132a (1,1-difluoroethene,CH₂═CF₂), TFE (tetrafluoroethene, CF₂═CF₂), HCFO-1122(2-chloro-1,1-difluoroethene, CHCl═CF₂), 3,4,4,4-tetrafluoro-2-butanone(CH₃C(═O)CHFCF₃), acetyl fluoride (CH₃C(═O)F),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH),2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃), zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl),2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate(CF₃CFClCH₂OCH₂C(═O)CH₃), 1,3-bistrifluoromethyl-1,3-difluorocyclobutane(C₆H₄F₈), 2,3,3,3-tetrafluoropropyl acetate (CF₃CHFCH₂C(═O)CH₃),dimethylformamide (DMF, HCON(CH₃)₂), pyridine (C₅H₅N), ethyl acetate,(CHClFCF₃), acetic acid (CH₃C(═O)OH), diethyl ether (CH₃CH₂OCH₂CH₃),acetic anhydride (CH₃C(═O)OC(═O)CH₃), methyl acetate (CH₃C(═O)OCH₃),dimethylacetamide (CH₃C(═O)N(CH₃)₂), methanol (CH₃OH), ethanolCH3CH2OH), methyl formate (HC(═O)OCH₃), pyrazine, pyrimidine,N-methylpyrrolidine, N-methylpiperidine, hexamethylphosphoramide,tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidinone, dimethyl sulfoxide,acetonitrile, benzonitrile, and mixtures thereof, meaning mixtures ofany of the foregoing additional compounds listed in this paragraph.

In another embodiment is provided a composition comprising2-chloro-3,3,3-trifluoropropanol (CF₃CClFCH₂OH), at least one solvent,and optionally at least one additional compound.

In another embodiment is provided a composition comprising2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃), atleast one solvent, and optionally at least one additional compound.

In another embodiment, is provided a composition comprising zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl), atleast one solvent, and optionally at least one additional compound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing showing different reactions for producingHFO-1234yf from CFC-114a.

DETAILED DESCRIPTION Compositions

A process for making 2,3,3,3-tetrafluoropropene (HFO-1234yf, CF₃CF═CH₂)from CFC-114a (or just 114a or CF₃CFCl₂) is shown in FIG. 1. As can beseen from FIG. 1, CF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃ and CF₃CClFCH₂OZnClare intermediate compounds which may be formed in this process.

Referring to FIG. 1, in one embodiment, CFC-114a may be reacted to formCF₃CFClCH₂OH, by treatment with activated zinc powder andparaformaldehyde. This reaction may be carried out in the liquid phasein the presence of a solvent. CF₃CFClCH₂OH may be reacted with acarboxylic acid anhydride (e.g. acetic anhydride) and a reactive metal(e.g. zinc) to form CF₃CClFCH₂OC(═O)CH₃, which may further be reacted insolvent with a reactive metal, such as zinc, to produce HFO-1234yf. Inone particular embodiment, the solvent may be a mixed solvent, such asDMF (dimethylformamide) and pyridine. However, it should be noted thatthe present invention is not limited to the use of these particularsolvents, and a variety of solvents, such as those listed below, infra,will work with the present invention.

Alternatively, in another embodiment, as shown in FIG. 1, CFC-114a maybe reacted with a reactive metal and an aldehyde to formCF₃CFClCH₂OZnCl. This reaction may also be carried out in the liquidphase in the presence of a solvent. Again, in one particular embodiment,the solvent may be a mixed solvent, such as DMF (dimethylformamide) andpyridine, it being noted that a variety of solvents, such as thoselisted below, infra, will work with the present invention.CF₃CFClCH₂OZnCl may be further reacted with a carboxylic acid anhydride(e.g. acetic anhydride) and a reactive metal (e.g., zinc) to formCF₃CClFCH₂OC(═O)CH₃, which may further be reacted in solvent with areactive metal, such as zinc, to produce HFO-1234yf. In yet anotherembodiment, all of the above mentioned reactions may be carried out inmultiple steps in a single reaction vessel wherein none of theintermediate compounds are isolated. This is indicated in FIG. 1 as asingle arrow from CFC-114a to HFO-1234yf.

2,3,3,3-tetrafluoropropene (HFO-1234yf, CF₃CF═CH₂),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH),2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃), andzinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl)may be prepared as described herein.

In one embodiment, the composition of the present invention comprisesHFO-1234yf and at least one additional compound selected from the groupconsisting of CFC-114a (2-dichloro-1,1,1,2-tetrafluoroethane, CCl₂FCF₃),shown in FIG. 1, HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane,CF₃CHFCl), HFC-143a (1,1,1-trifluoroethane, CF₃CH₃), CFO-1113(2-chloro-1,1,2-trifluoroethene, CClF═CF₂), HFO-1123(1,1,2-trifluoroethene, CHF═CF₂), HFO-1132a (1,1-difluoroethene,CH₂═CF₂), TFE (tetrafluoroethene, CF₂═CF₂), HCFO-1122(2-chloro-1,1-difluoroethene, CHCl═CF₂), 3,4,4,4-tetrafluoro-2-butanone(CH₃C(═O)CHFCF₃), acetyl fluoride (CH₃C(═O)F),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH), shown in FIG. 1,2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃), shownin FIG. 1, zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride(CF₃CClFCH₂OZnCl), shown in FIG. 1, 2-chloro-2,3,3,3-tetrafluoropropoxymethyl acetate (CF₃CFClCH₂OCH₂C(═O)CH₃),1,3-bistrifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈),2,3,3,3-tetrafluoropropyl acetate (CF₃CHFCH₂C(═O)CH₃), dimethylformamide(DMF, HCON(CH₃)₂), pyridine (C₅H₅N), ethyl acetate, (CHClFCF₃), aceticacid (CH₃C(═O)OH), diethyl ether (CH₃CH₂OCH₂CH₃), acetic anhydride(CH₃C(═O)OC(═O)CH₃), methyl acetate (CH₃C(═O)OCH₃), dimethylacetamide(CH₃C(═O)N(CH₃)₂), methanol (CH₃OH), ethanol CH3CH2OH), methyl formate(HC(═O)OCH₃), pyrazine, pyrimidine, N-methylpyrrolidine,N-methylpiperidine, hexamethylphosphoramide, tetrahydrofuran,1,4-dioxane, N-methylpyrrolidinone, dimethyl sulfoxide, acetonitrile,benzonitrile, and mixtures thereof, meaning mixtures of any of theforegoing additional compounds listed in this paragraph. Any of thecompositions of this embodiment as set forth in this paragraph will bereferred to hereinafter as Composition A. These compositions can beeither vapor phase or liquid phase compositions.

FIG. 1 is a representative illustration of the process for making thecompositions of the present invention, and not all of the additionalcompounds listed in the paragraph above are shown in FIG. 1, it beingunderstood that the composition of the present invention may include allof these additional compounds. The additional compounds listed here aspotentially being in the composition comprising HFO-1234yf may bepresent in the starting materials or the solvent, or these additionalcompounds may be the reaction products of such additional compoundswhich are present in the starting materials, produced under theconditions of the reactions to make the HFO-1234yf.

The reaction chemistry described herein and illustrated in FIG. 1produces HFO-1234yf containing no detectable HFO-1234ze(1,3,3,3-tetrafluoropropene), i.e., it is “essentially free” ofHFO-1234ze. By “essentially free of” is meant that the amount ofHFO-1234ze present is essentially zero. The ability to detect thepresence of any component depends upon the analytical method used andvarious other factors. In one embodiment, essentially free of HFO-1234zemeans that the composition contains less than 10 parts per million (ppm)by weight HFO-1234ze. In another embodiment, essentially free ofHFO-1234ze means that the composition contains less than 5 ppm by weightHFO-1234ze. In another embodiment, essentially free of HFO-1234ze meansthat the composition contains less than 1 ppm by weight HFO-1234ze.

In one embodiment, the total amount of additional compound(s) in thevapor phase of the composition comprising HFO-1234yf ranges from greaterthan zero weight percent to about 30 weight percent. In anotherembodiment, the total amount of additional compounds ranges from greaterthan zero weight percent to about 20 weight percent. In anotherembodiment, the total amount of additional compound(s) ranges fromgreater than zero weight percent to about 10 weight percent. In anotherembodiment, the total amount of additional compound(s) ranges fromgreater than zero weight percent to about 5 weight percent.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising HFO-1234yf ranges from greater than zero weightpercent to less than 1 weight percent.

In some embodiments, certain precursor compounds to HFO-1234yf containimpurities that appear as the additional compounds in the HFO-1234yfcompositions. In other embodiments, the additional compounds are formedby reaction of these precursor impurities. In other embodiments, thereaction conditions under which the HFO-1234yf is produced also produceby-products that then appear as the additional compounds in theHFO-1234yf compositions, by which is meant alternative reaction pathwaysmay produce additional compounds depending upon the particularconditions under which the HFO-1234yf is produced.

In another particular embodiment, the composition of the presentinvention comprises HFO-1234yf and the following additional compounds:tetrafluoroethene, 1,1-difluoroethene, trifluoroethene, and2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124). A representative amountof impurities for this embodiment is about 80 weight % 1234yf, about 10weight % HCFC-124 and the remainder being the tetrafluoroethene,1,1-difluoroethene, trifluoroethene.

In another particular embodiment, the composition of the presentinvention comprises HFO-1234yf and the following additional compounds:2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH), acetic anhydride,methyl acetate, DMF, and pyridine. In this embodiment, there is greaterthan 90 weight % 1234yf, about 2 weight % pyridine, and about 1 weight %or less of the remaining additional compounds.

In another particular embodiment, the composition of the presentinvention comprises HFO-1234yf and the following additional compounds:tetrafluoroethene (TFE), HFO-1123, 1,1,1-trifluoroethane (HFC-143a),CFO-1113, HCFC-124, CFC-114a,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, aceticacid, and 2,3,3,3-tetrafluoropropyl acetate. In this embodiment, arepresentative amount of impurities is about 10 weight % or less ofHFO-1123, HCFC-124, and 1,3-bis-trifluoromethyl-1,3-difluorocyclobutane;and less than about 1 weight of the remainder.

In another particular embodiment, the composition of the presentinvention comprises HFO-1234yf and the following additional compounds:HFO-1123, water, CFO-1113,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, andmethyl acetate. In this embodiment, a representative amount ofimpurities is about 1 weight % or less of HFO-1123, water, CFO-1113,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, andmethyl acetate.

In another embodiment, the present disclosure provides a compositioncomprising either 1) 2-chloro-2,3,3,3-tetrafluoropropanol(CF₃CClFCH₂OH), or 2) CF₃CClFCH₂OC(═O)CH₃; or 3) CF₃CClFCH₂OZnCl, andeach including at least one solvent. The composition comprising2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) and at least onesolvent shall be referred to hereinafter as Composition B. Thecomposition comprising 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃) and at least one solvent shall be referred tohereinafter as Composition C. The composition comprising zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl) and atleast one solvent shall be referred to hereinafter as Composition D.

In one embodiment, the total amount of additional compound(s) in thecompositions comprising CF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃, orCF₃CClFCH₂OZnCl and at least one solvent ranges from greater than zeroweight percent to about 50 weight percent based upon the totalcomposition. In another embodiment, the total amount of additionalcompounds ranges from greater than zero weight percent to about 30weight percent. In another embodiment, the total amount of additionalcompound(s) ranges from greater than zero weight percent to about 10weight percent. In another embodiment, the total amount of additionalcompound(s) ranges from greater than zero weight percent to about 5weight percent. In another embodiment, the total amount of additionalcompound(s) ranges from greater than zero weight percent to about 1weight percent.

In some embodiments, certain precursor compounds to CF₃CClFCH₂OH,CF₃CClFCH₂OC(═O)CH₃, or CF₃CClFCH₂OZnCl contain impurities that appearin the CF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃, or CF₃CClFCH₂OZnCl. In otherembodiments, the additional compounds are formed by reaction of theseprecursor impurities. In other embodiments, the reaction conditionsunder which the CF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃, or CF₃CClFCH₂OZnCl isproduced also produce by-products, by which is meant alternativereaction pathways may produce additional compounds depending upon theparticular conditions under which the CF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃,or CF₃CClFCH₂OZnCl is produced. For these products as produced by theprocesses described herein, certain other compounds introduced by way ofthe solvent used to carry out the chemistry may be present in thecompositions or may react to form other compounds that may be present inthe compositions as well.

In one embodiment, the solvent is selected from the group consisting ofalkyl, dialkyl, and trialkyl linear or cylic amines,N-methylpyrrolidine, N-methylpiperidine, sulfoxides, ethers, pyridine oralkyl-substituted pyridines, pyrazine or pyrimidine, alkyl and aromaticnitriles, hexamethylphosphoramide, and mixtures thereof. In anotherembodiment, the solvent is selected from the group consisting oftrialkylamines, N-methylpyrrolidine, N-methylpiperidine, pyridine,alkyl-substituted pyridines, dimethylformamide, pyrazine or pyrimidine,and mixtures thereof. In another embodiment, the reaction solvent isselected from the group consisting of dimethylformamide,tetrahydrofuran, pyridine, dimethylacetamide, 1,4-dioxane,N-methylpyrrolidone, diethyl ether and mixtures thereof. In anotherembodiment, the solvent is pyridine or alkyl-substituted pyridines ormixtures thereof. In another embodiment, the solvent is selected fromthe group consisting of alcohols, esters, and mixtures thereof. Inanother embodiment, the solvent is selected from the group consisting ofmethanol, ethanol, methyl formate, dimethyl sulfoxide, acetonitrile,benzonitrile and mixtures thereof, or mixtures of these with any of theaforementioned other solvents.

In one embodiment, the total amount of solvent present in thecompositions comprising any of CF₃CClFCH₂OH, CF₃CClFCH₂OZnCl, orCF₃CClFCH₂OC(═O)CH₃, will vary depending upon various factors. If notenough solvent is provided not all of the reactant and/or productcompounds will stay in solution. Additionally, if too much solvent isused, the rate of reaction will be slow. In one embodiment, the solventwill be present in an amount of at least about 90 weight percent of thecomposition. In another embodiment, the solvent will be present in thecompositions in an amount of at least 50 weight percent of thecomposition. In another embodiment, the solvent will be present in thecompositions in an amount of at least about 30 weight percent of thecomposition. In yet another embodiment the solvent will be present in anamount of at least about 20 weight percent.

In another embodiment, the composition comprising CF₃CClFCH₂OH and atleast one solvent may further comprise at least one additional compoundselected from the group consisting of HFO-1234yf, CFC-114a, HCFC-124,CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, dimethylacetamide,methanol, methyl acetate, methyl formate, dimethylformamide, pyridine,ethyl acetate, acetic acid, diethyl ether, CF₃CClFCH₂OZnCl,CF₃CClFCH₂OC(═O)CH₃, 2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate,and mixtures thereof meaning mixtures of any of the foregoing additionalcompounds listed in this paragraph. It is noted that not all of thecompounds listed here are shown in FIG. 1, since FIG. 1 is meant to be arepresentative illustration of the processes to make the compositions ofthe present invention. It is believed that these compounds arise asimpurities in the starting materials, impurities in the solvent, oreither of these types of impurities that have reacted to form othercompounds under the reaction conditions used to produce theCF₃CClFCH₂OH. The compositions of this embodiment as described in thisparagraph will be referred to hereinafter as Compositions B(1).

In one particular embodiment, the composition comprises2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) and at least onesolvent comprising dimethylformamide and further comprises HCFC-124 andmethanol as the additional compounds. In this embodiment, the solvent,DMF, may be present at about 80 weight % or higher. The HCFC-124 may beat about 8 weight % or less and the methanol may be less than about 1weight %.

In another particular embodiment, the composition comprising2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) and at least onesolvent comprising pyridine, and further comprises2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), methyl formate,chlorotrifluoroethene (CFO-1113), trifluoroethene (HFO-1123) andmethanol as the additional compounds. In this embodiment, the pyridinesolvent is present at about 80 weight % or more, HCFC-124 is present atabout 3 weight % or less and the other additional compounds are each atabout 1 weight % or less.

In another particular embodiment, the composition comprising2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) and at least onesolvent comprising dimethylacetamide and further comprises2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), methyl formate,chlorotrifluoroethene (CFO-1113), and trifluoroethene (HFO-1123), andmethanol as the additional compounds. A representative amount of theadditional compounds for this embodiment is about 2-3 weight % each ofHCFC-124 and CFO-1113 and about 1 weight % or less of the remainingcompounds.

In another embodiment, the composition comprising CF₃CClFCH₂OC(═O)CH₃and at least one solvent may further comprise at least one additionalcompound selected from the group consisting of HFO-1234yf, CFC-114a,HCFC-124, CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, methanol,methyl acetate, methyl formate, dimethylacetamide, dimethylformamide,pyridine, ethyl acetate, acetic acid, diethyl ether, acetic anhydride,formaldehyde, 3-chloro-3,4,4,4-trifluoro-2-butanone,2,3,3,3-tetrafluoropropyl acetate, CF₃CClFCH₂OCH(═O),2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate, CF₃CClFCH₂OH,CF₃CClFCH₂OZnCl, and mixtures thereof, meaning mixtures of any of theforegoing additional compounds listed in this paragraph. The compositionof the present invention as described in this paragraph will be referredto hereinafter as Composition C(1). Again, it is noted that not all ofthe compounds listed here are shown in FIG. 1. It is believed that thesecompounds arise as impurities in the starting materials, impurities inthe solvent, or either of these types of impurities that have reacted toform other compounds under the reaction conditions used to produce theCF₃CClFCH₂OC(═O)CH₃.

In one particular embodiment where the composition of the presentinvention comprises 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃), at least one solvent comprising diethyl ether andadditional compounds, the additional compounds comprise2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH), ethyl acetate, andacetic acid. A representative amount of the additional compounds forthis embodiment is about 17 weight % acetic acid, about 3 weight % ethylacetate, and less than about 1 weight %2-chloro-2,3,3,3-tetrafluoropropanol, all of which are relative to theamount of the 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃) in the composition.

In one other particular embodiment where the composition of the presentinvention comprises 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃), at least one solvent which is DMF and pyridineand additional compounds, the additional compounds comprise2-chloro-2,3,3,3-tetrafluoropropyl formate (CF₃CClFCH₂OCH(═O)),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) acetic anhydride andacetic acid. In this embodiment, the solvent is a mixture of and DMF andpyridine. A representative amount of the additional compounds for thisembodiment is about 3 weight % or less for all the additional compounds.

In one particular embodiment where the composition of the presentinvention comprises 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃), at least one solvent, which is DMF and pyridine,and additional compounds, the additional compounds comprise TFE,HCFC-124, 3-chloro-3,4,4,4-trifluoro-2-butanone (CF₃CClFCH₂OC(═O)CH₃),ethyl methyl ether, and methyl acetate, all in the liquid phase. In thisembodiment, the solvent is a mixture of DMF and pyridine. Arepresentative amount of the additional compounds for this embodiment isabout 85 weight % 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃), about 6 weight % of 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), about 2.5 weight %3-chloro-3,4,4,4-trifluoro-2-butanone (CF₃CClFCH₂OC(═O)CH₃), about 2.5weight unknowns, and less than 1 weight % each of TFE, ethyl methylether and methyl acetate.

In another particular embodiment, where the composition of the presentinvention comprises 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃), at least one solvent, which in this case is amixture of DMF and pyridine, and additional compounds, the additionalcompounds comprise HFO-1123, HFO-1234yf, water, formaldehyde, HCFC-124,CFC-114a, methyl acetate, methyl formate,3-chloro-3,4,4,4-tetrafluoro-2-butanone, 2,3,3,3-tetrafluoropropylacetate, 2-chloro-2,3,3,3-tetrafluoropropanol, acetic anhydride, and2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate. A representativeamount of the additional compounds for this embodiment is about 6-8weight % each of HCFC-124, and 2-chloro-2,3,3,3-tetrafluoropropoxymethyl acetate: about 1-4 weight % each of water, CFC-114a,3-chloro-3,4,4,4-tetrafluoro-2-butanone,2-chloro-2,3,3,3-tetrafluoropropanol, and acetic anyhydride; and lessthan about 1 weight % of the remainder.

In another particular embodiment, where the composition of the presentinvention comprises 2-chloro-2,3,3,3-tetrafluoropropyl acetate(CF₃CClFCH₂OC(═O)CH₃), at least one solvent, which is DMF and pyridine,and additional compounds, the additional compounds comprise HCFC-124,CFC-114a, methyl acetate, ethyl formate, methyl formate, acetic acid,3-chloro-3,4,4,4-tetrafluoro-2-butanone,2-chloro-2,3,3,3-tetrafluoropropanol, acetic anyhydride, and2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate. A representativeamount of the additional compounds for this embodiment is about 7-8weight % of 2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate; about 3weight % of HCFC-124; and less than about 2 weight % of the remainder.

In another embodiment, the composition comprising CF₃CClFCH₂OZnCl and atleast one solvent may further comprise at least one additional compoundselected from the group consisting of HFO-1234yf, CFC-114a, HCFC-124,CFO-1113, HFO-1123, HFO-1132a, TFE, HCFO-1122, methanol, methyl acetate,methyl formate, dimethylacetamide, dimethylformamide, pyridine, ethylacetate, acetic acid, diethyl ether, formaldehyde,trifluoroacetaldehyde, CF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃,2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate(CF₃CFClCH₂OCH₂C(═O)CH₃), and mixtures thereof, meaning mixtures of anyof the foregoing additional compounds listed in this paragraph. Thecomposition of the present invention as described in this paragraph willbe referred to hereinafter as Composition D(1). Again, it is noted thatnot all of the compounds listed here are shown in FIG. 1. It is believedthat these compounds arise as impurities in the starting materials,impurities in the solvent, or either of these types of impurities thathave reacted to form other compounds under the reaction conditions usedto produce the CF₃CClFCH₂OZnCl.

In one particular embodiment, the composition comprising zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl) and atleast one solvent comprising pyridine further comprises2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), methyl formate, methanoland trifluoroethene (HFO-1123) as the additional compounds. In thisembodiment, the solvent is pyridine. In this particular embodiment, thecomposition comprises about 80 weight % or more of solvent, that beingpyridine, about 12 weight % or more zinc(2-chloro-2,3,3,3-tetrafluoropropoxide) chloride (CF₃CClFCH₂OZnCl about3 weight % HCFC-124, and 1 weight % or less of the remaining components,those being methyl formate, methanol, and HFO-1123.

In another particular embodiment, the composition comprising zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl) and atleast one solvent comprising a mixture of DMF and pyridine furthercomprises tetrafluoroethene, acetic acid, methyl formate, methylacetate, HCFC-124, HFO-1234yf, and 2-chloro-2,3,3,3-tetrafluoropropylacetate (CF₃CClFCH₂OC(═O)CH₃) as additional compounds. In thisparticular embodiment, the HCFC-124, CF₃CClFCH₂OC(═O)CH₃, and theHFO-1234yf are each present at about 3-5 weight % relative to theCF₃CClFCH₂OZnCl.

In another particular embodiment, the composition comprising zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl) and atleast one solvent comprising a mixture of DMF and pyridine furthercomprises HFO-1123, trifluoroacetaldehyde, formaldehyde, HCFC-124,CFC-114a, methanol, methyl formate, and2-chloro-2,3,3,3-tetrafluoropropyl acetate as additional compounds. Inthis embodiment, the HCFC-124 is present at about 13 weight % or lessrelative to the amount of zinc (2-chloro-2,3,3,3-tetrafluoropropoxy)chloride (CF₃CClFCH₂OZnCl), and the remaining additional compounds arepresent at 1 weight % or less.

In another particular embodiment, the composition comprisingzinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl) andat least one solvent comprising a mixture of DMF and pyridine furthercomprises HFO-1123, trifluoroacetaldehyde, HFO-1234yf, formaldehyde,HCFC-124, CFC-114a, methanol, dimethyl ether, methyl formate, ethylformate, 2-chloro-2,3,3,3-tetrafluoropropyl acetate, and aceticanhydride as additional compounds. In this embodiment, the HCFC-124 waspresent at about 8 weight %, and the other additional compounds wereeach present at about 2 weight % or less.

Certain components of the disclosed compositions are commerciallyavailable, such as for instance the solvents. Other components may beprepared by methods known in the art. HFO-1234yf, CF₃CClFCH₂OH,CF₃CClFCH₂OZnCl and CF₃CClFCH₂OC(═O)CH₃ may be prepared as describedherein below.

The compositions as disclosed herein may be prepared by the reactionchemistry described below.

Reaction Chemistry

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, formaldehyde refers to the compound having the structureH₂C═O, which is also known to occur in the form of a cyclic trimer1,3,5-trioxane, and also as paraformaldehyde or polyoxymethylene(sometimes shown as (H2C═O)_(n)).

As used herein, reactive metal refers to reactive metals such asmagnesium turnings, activated zinc powder, aluminum, and a powder of anyof the following metals: magnesium, calcium, titanium, iron, cobalt,nickel, copper, zinc and indium, and also zinc(II) salts. Magnesiumturnings are pieces of magnesium which are cut to produce small pieceswith higher surface areas and generally low amounts of surface oxides(which reduce reactivity). The reactive metal powders of magnesium,calcium, titanium, iron, cobalt, nickel, copper, zinc and indium areRieke metals, which are prepared by a specific procedure which produceshigh surface area metal powders which are very reactive in reactionssuch as those of the present invention. Without wishing to be bound byany particular theory, Rieke metals are thought to be highly reactivebecause they have high surface areas and lack passivating surfaceoxides.

As used herein, a dehydrating agent is a gas or gaseous mixturecontaining at least one gas selected from the group consisting of:methane, ethane, propane, butane, natural gas, alcohols, aldehydes, andcarbon monoxide. As used herein, natural gas refers to a gaseous mixturehaving methane as the major component, but also comprising quantities ofethane, butane, propane, carbon dioxide, nitrogen.

As used herein dehydroxychlorinating refers to removing a hydroxyl groupand a chlorine atom from adjacent carbon atoms of a hydrofluoroalkanolto form a hydrofluoroalkene.

In one embodiment, 2-chloro-1,1,1,2-tetrafluoropropanol (CF₃CClFCH₂OH)may be prepared by reaction of a CFC-114a with an aldehyde, and areactive metal in a reaction solvent, thus producing2-chloro-1,1,1,2-tetrafluoro-propanol (CF₃CClFCH₂OH) and a solvent. Themethod as described in this paragraph produces Composition B asdescribed above.

Alternatively, CFC-114a is reacted with an aldehyde, and a reactivemetal in a reaction solvent to generate a composition a metalhydrofluoroalkoxide, CF₃CFClCH₂OZnCl and a solvent. The method asdescribed in this paragraph produces Composition D as described above.

The metal hydrofluoroalkoxide may be neutralized to provide ahydrofluoroalkanol, CF₃CClFCH₂OH, which can be isolated. Theneutralization may comprise dilution with an organic solvent, andreaction with a dilute aqueous solution of an acid, including withoutlimitation dilute aqueous hydrochloric acid or dilute aqueous sulfuricacid. Upon separation of the organic solvent phase from the aqueousphase, the organic solvent phase is washed further with an aqueous saltsolution. The organic solvent phase is then dried and the solventremoved by evaporation or distillation to provide the hydrofluoroalkanolproduct.

Additionally, the metal hydrofluoroalkoxide, CF₃CClFCH₂OZnCl, may beused in further reactions as described later to produce ahydrofluoroalkene, HFO-1234yf, without neutralization. The method asdescribed in this paragraph produces Composition A as described above.

In addition to the reactive metal, (i.e., just the zinc), a metal saltmay be added to the mixture comprising the reaction of the CFC-114a.Suitable zinc salts include zinc acetate, zinc bromide, zinc chloride,zinc citrate, zinc sulfate and mixtures thereof. In one embodiment, thezinc salt is zinc acetate. The amount of zinc salt added may be from 0.1to 1.0 mole per mole of CFC-114a. The aldehyde for reaction withCFC-114a may be selected from the group consisting of formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde. Themole ratio of reactive metal to CFC-114a is from about 1:1 to about2.5:1. The mole ratio of aldehyde to CFC-114a is from about 1:1 to about3:1.

In some embodiments, wherein paraformaldehyde is used as the aldehyde, aquaternary ammonium salt is added to the reaction. In one embodiment,the quaternary ammonium salt is a bis-alkyldimethyl ammonium acetate.Without wishing to be bound by any particular theory, such quaternaryammonium salts are believed to promote the decomposition ofparaformaldehyde to formaldehyde. In some embodiments the amount ofquaternary ammonium salt added is from about 1 weight % to about 20weight % by weight of the amount of paraformaldehyde. In otherembodiments, the amount of quaternary ammonium salt added is from about5 weight % to about 10 weight % by weight of the amount ofparaformaldehyde.

The reaction of CFC-114a with an aldehyde and reactive metal isconducted in a reaction solvent. The reaction solvent may be selectedfrom the group consisting of alkyl, dialkyl, and trialkyl linear orcylic amines, N-methylpyrrolidine, N-methylpiperidine, sulfoxides,ethers, pyridine or alkyl-substituted pyridines, pyrazine or pyrimidine,alkyl and aromatic nitriles, hexamethylphosphoramide, and mixturesthereof. In another embodiment, the solvent is selected from the groupconsisting of trialkylamines, N-methylpyrrolidine, N-methylpiperidine,pyridine, alkyl-substituted pyridines, dimethylformamide, pyrazine orpyrimidine, and mixtures thereof. In another embodiment, the reactionsolvent is selected from the group consisting of dimethylformamide,tetrahydrofuran, pyridine, dimethylacetamide, 1,4-dioxane,N-methylpyrrolidone, diethyl ether and mixtures thereof. In anotherembodiment, the solvent is pyridine or alkyl-substituted pyridines ormixtures thereof. In another embodiment, the solvent is selected fromthe group consisting of alcohols, esters, and mixtures thereof. Inanother embodiment, the solvent is selected from the group consisting ofmethanol, ethanol, methyl formate, dimethyl sulfoxide, acetonitrile,benzonitrile and mixtures thereof, or mixtures of these with any of theaforementioned other solvents.

The amount of water present in the reaction of CFC-114a with an aldehydeand reactive metal may be less than 1000 ppm. The reaction of CFC-114awith an aldehyde and reactive metal is performed at a temperature offrom about 30° C. to about 100° C., and the reaction is conducted forfrom about 3 to about 10 hours. The aldehyde may be pre-treated with thereaction solvent for a period of time before the reaction. For instance,paraformaldehyde is pre-treated in pyridine for four hours at 60° C.prior to reaction with CFC-114a and reactive metal. The pre-treatmentmay occur for two to six hours or there may be no pre-treatment, and thereaction may be commenced upon charging all of the reactants andreaction solvent to the reaction vessel sequentially.

The reaction of CFC-114a with an aldehyde and reactive metal may beperformed in a closed vessel or other reactor. The reaction may beperformed under autogenous pressure. Alternatively, the reaction ofCFC-114a with an aldehyde and reactive metal may be performed in an openvessel or reactor, equipped with a suitable condenser to prevent escapeof unreacted CFC-114a.

Another process for the manufacture of HFO-1234yf comprises reactingCFC-114a with an aldehyde and zinc metal to generate CF₃CClFCH₂OZnCl andthen reductively dehydroxychlorinating CF₃CClFCH₂OZnCl in a second stepto produce HFO-1234yf. The process for producing HFO-1234yf may compriseneutralizing CF₃CClFCH₂OZnCl to produce CF₃CClFCH₂OH; mixing adehydrating agent with CF₃CClFCH₂OH, thereby forming a gaseous mixture;and contacting a catalyst with the gaseous mixture, thereby formingHFO-1234yf. The gaseous mixture is a mixture of the dehydrating agentand hydrofluoroalkanol, mixed in the gas phase.

The reaction product of CFC-114a, an aldehyde and a reactive metal maybe neutralized by diluting the reaction product mixture with a mixtureof a solvent, ice, and an aqueous solution of an acid. The solvent canbe any commonly used organic solvent, such as diethyl ether. The aqueoussolution of an acid may be an aqueous solution of a common mineral acid,such as hydrochloric acid. After stirring the resulting mixture for aperiod of time, the layer comprising the organic solvent is separated.The organic solvent layer can be subsequently washed with a diluteaqueous solution of an acid, followed by a brine solution. The organiclayer is then dried. The drying is accomplished by stirring the organiclayer over an anhydrous salt, such as anhydrous magnesium sulfate oranhydrous sodium sulfate. The organic solvent may then be evaporated toafford CF₃CClFCH₂OH.

The catalyst is at least one transition metal. The metal is selectedfrom the group consisting of: Ni, Pd, and Pt. In one embodiment, thecatalyst is a supported catalyst which comprises a transition metal anda support material. The support material is at least one selected fromthe group consisting of activated carbon and γ-alumina.

The dehydrating agent is at least one gas selected from the groupconsisting of: methane, ethane, propane, butane, natural gas, alcohols,aldehydes, and carbon monoxide.

The mixing step takes place at a temperature in the range between about65-80° C.

The gaseous mixture may be preheated prior to the contacting step. Thepreheating takes place at a temperature in the range between about 250to about 450° C.

The contacting step preferably takes place at a temperature in the rangebetween about 400 to about 700° C. The contacting step also preferablytakes place for between about 20 to about 25 seconds.

Residual HF contained in the HFO-1234yf product may then be neutralized,wherein the HF is neutralized by passing the HFO-1234yf product througha KOH solution. Alternatively, HF may be removed from the HFO-1234yfproduct by some other method known in the art, including for instanceazeotropic distillation.

The gaseous mixture may further comprise at least one diluent inert gasselected from the group consisting of: nitrogen, helium, and argon.

The conversion of the CF₃CClFCH₂OH to HFO-1234yf is in the range betweenabout 50 to about 100%. The selectivity of CF₃CClFCH₂OH to HFO-1234yf isin the range between about 29 to about 100%.

The pressure during the contacting step is in the range between about 1to about 100 psig.

The reductive dehydroxychlorination may be carried out by reacting theCF₃CClFCH₂OZnCl, described earlier as Composition D, or CF₃CClFCH₂OH,described earlier as Composition B, with a carboxylic acid anhydride anda reactive metal in a reaction solvent to form a hydrofluoroalkene.Either of CF₃CClFCH₂OZnCl or CF₃CClFCH₂OH will react with the acidanhydride to produce an ester, CF₃CClFCH₂OC(═O)CH₃, which is thenreduced by the reactive metal to produce HFO-1234yf. This 1234yfcomposition contains additional compounds as described earlier asComposition A.

This reaction may be run as described with addition of both reagents inthe same reaction vessel or the acid anyhydride may be added alone toproduce CF₃CClFCH₂OC(═O)CH₃, which may be isolated. And then thereactive metal may be added to the CF₃CClFCH₂OC(═O)CH₃ to produce theHFO-1234yf. In this process the carboxylic acid anhydride is selectedfrom the group consisting of acetic anhydride, propionic anhydride,butyric anhydride, succinic anhydride, glutaric anhydride, and adipicanhydride. The reactive metal powder is as described previously herein.The reductive dehydroxychlorination can be done without neutralizing theproduct mixture from the reaction of CFC-114a with zinc and an aldehyde.Or the reductive dehydroxychlorination may be done after first isolatingthe CF₃CClFCH₂OH, and then esterification by reaction with a carboxylicacid anhydride and a reactive metal to form CF₃CClFCH₂OC(═O)CH₃. Any ofthese dehydroxychlorinations produce Composition C as described above.

In some embodiments, the product of the reductive dehydroxychlorinationis HFO-1234yf as described above, which further comprises1,3-bistrifluoromethyl-1,3-difluorocyclobutane, a substitutedcyclobutane of the formula:

This compounds may also be represented by the formula:cyclo-(—CH₂(CF₃)CFCH₂(CF₃)CF—)-.

The carboxylic acid anhydride may be acetic anhydride. The mole ratio ofacetic anhydride to CF₃CClFCH₂OH is from about 1:1 to about 2:1. Themole ratio of reactive metal to CF₃CClFCH₂OH is from about 1:1 to about2.5:1. The reductive dehydroxychlorination may be conducted in areaction solvent which is the same solvent that the reaction of CFC-114awith reactive metal and an aldehyde is conducted in or a differentsolvent.

The reaction chemistry disclosed herein that produces the compositionsdisclosed herein is particularly useful in producing HFO-1234yf withoutproducing HFO-1234ze (1,3,3,3-tetrafluoropropene, E- or Z-isomer). Thisresults in a product, HFO-1234yf, which is essentially free ofHFO-1234ze, as described above. Other common processes known forproduction of HFO-1234yf involve dehydrofluorination of saturatedcompounds such as 1,1,1,2,2-pentafluoropropane (HFC-245cb) and/or1,1,1,2,3-pentafluoropropane (HFC-245eb). This dehydrofluorinationchemistry regardless of whether accomplished liquid phase by reactionwith caustic or vapor phase by a thermal and/or catalytic processproduces percent quantities of HFO-1234ze. The presence of this compoundhas not been acceptable to the refrigerants industry as it causesdecreasing performance in refrigeration and air conditioning systems ofall types. Therefore, extensive distillation processes must be added tothe back end of any commercial manufacturing facility utilizing thischemistry to allow the removal of HFO-1234ze from the productHFO-1234yf. Therefore any chemistry that can produce HFO-1234yfessentially free of HFO-1234ze has a great advantage in the industry.

Utility

The compositions disclosed herein comprising HFO-1234yf are useful aslow global warming potential (GWP) heat transfer compositions, aerosolpropellant, foam expansion agents (also known as foaming agents orblowing agents), solvents, cleaning agents, carrier fluids, displacementdrying agents, buffing abrasion agents, polymerization media, expansionagents for polyolefins and polyurethane, gaseous dielectrics,extinguishing agents, and fire suppression agents in liquid or gaseousform. The disclosed compositions can act as a working fluid used tocarry heat from a heat source to a heat sink. Such heat transfercompositions may also be useful as a refrigerant in a cycle wherein thefluid undergoes a phase change; that is, from a liquid to a gas and backor vice versa.

Examples of heat transfer systems include but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,heat pumps, mobile refrigerators, mobile air conditioning units andcombinations thereof.

In one embodiment, the compositions comprising HFO-1234yf are useful inmobile heat transfer systems, including refrigeration, air conditioning,or heat pump systems or apparatus. In another embodiment, thecompositions are useful in stationary heat transfer systems, includingrefrigeration, air conditioning, or heat pump systems or apparatus.

As used herein, mobile heat transfer systems refers to anyrefrigeration, air conditioner, or heating apparatus incorporated into atransportation unit for the road, rail, sea or air. In addition, mobilerefrigeration or air conditioner units, include those apparatus that areindependent of any moving carrier and are known as “intermodal” systems.Such intermodal systems include “containers” (combined sea/landtransport) as well as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems that arefixed in place during operation. A stationary heat transfer system maybe associated within or attached to buildings of any variety or may bestand alone devices located out of doors, such as a soft drink vendingmachine. These stationary applications may be stationary airconditioning and heat pumps (including but not limited to chillers, hightemperature heat pumps, residential, commercial or industrial airconditioning systems, and including window, ductless, ducted, packagedterminal, chillers, and those exterior but connected to the buildingsuch as rooftop systems). In stationary refrigeration applications, thedisclosed compositions may be useful in equipment including commercial,industrial or residential refrigerators and freezers, ice machines,self-contained coolers and freezers, flooded evaporator chillers, directexpansion chillers, walk-in and reach-in coolers and freezers, andcombination systems. In some embodiments, the disclosed compositions maybe used in supermarket refrigerator systems.

The compositions disclosed herein comprising CF₃CClFCH₂OH; and at leastone solvent are useful in methods to prepare HFO-1234yf as describedpreviously herein.

The compositions disclosed herein comprising CF₃CClFCH₂OC(═O)CH₃; and atleast one solvent are useful in methods to prepare HFO-1234yf asdescribed previously herein.

The compositions disclosed herein comprising CF₃CClFCH₂OZnCl; and atleast one solvent are useful in methods to prepare HFO-1234yf asdescribed previously herein.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following specific embodiments are, therefore, to beconstrued as merely illustrative, and do not constrain the remainder ofthe disclosure in any way whatsoever.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims. The results as given in GC or GC-MS area percent are thought toapproximate weight percent.

Example 1

Example 1 demonstrates the preparation of2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) from1,1,1,2-tetrafluoro-2,2-dichloroethane (CFC-114a), and the particularreaction products obtained from this preparation.

A 400 ml Hastelloy™ C shaker tube was charged with 32.8 grams (0.5 mole)of activated Zinc powder, 12 grams (0.5 mole) of paraformaldehyde and180 ml anhydrous dimethylformamide (DMF) under N₂. The tube was cooleddown to −15° C. and 64.4 grams (0.2 mole) of1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a) was added. Then thereaction mixture was stirred at 50° C. for 6 hours. The results of gaschromatographic analysis of the reaction products are summarized inTable 1. The reaction mixture was cooled to room temperature and thenpoured into a 200 mL mixture of ice, 10% aqueous HCl and 200 mL diethylether. The solution was stirred for 30 min and the organic layer wasseparated and washed with 100 mL of 2% aqueous HCl and then 100 mLbrine. The organic layer was dried with MgSO₄, and diethyl ether wasremoved by vacuum to afford 13.36 grams of product2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH), thus obtaining an8% yield.

TABLE 1 GC area Component percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 7.076 (CF₃CClFCH₂OH)2-chloro-1,1,1,2-tetrafluoroethane 8.18 (HCFC-124) Methanol 0.335 DMF83.9

Example 2

Example 2 demonstrates the synthesis of 2,3,3,3-tetrafluoropropene from1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), and the particularreaction products obtained from this synthesis.

A 400 ml Hastelloy™ C shaker tube was charged with 20 grams (0.315 mole)of activated zinc powder, 7.5 grams (0.25 mole) of paraformaldehyde and130 mL anhydrous DMF under N₂. The tube was cooled to −15° C., and 43grams (0.25 mole) of 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a)were added. The reaction mixture was stirred at 60° C. for 6 hours andthen cooled to room temperature. 30 grams (0.46 mole) of activated zincpowder, and 50 grams (0.5 mole) of acetic anhydride were added to thereactor. The reaction mixture was stirred at 50° C. for 6 hr and thencooled to room temperature. The gas phase and the liquid phase wereanalyzed by gas chromatography-mass spectrometry (GC-MS) Results aresummarized in Table 2. The 1234yf composition is demonstrated in the gasphase portion of Table 2 below, and the liquid phase portion of Table 2is what is left in the reactor when the gas sample comes off. Note thatthe gas phase sample corresponds to the compositions comprisingHFO-1234yf and additional compounds.

TABLE 2 GC area percent (%) Component (liquid phase remaining in thereactor after reaction) 2,3,3,3-tetrafluoropropene 5.50 (HFO-1234yf)2-chloro-1,1,1,2-tetrafluoroethane 16.93 (HCFC-124)3,4,4,4-tetrafluoro-2-butanone 3.7 Acetyl fluoride 4.57 Methyl acetate4.72 Acetic acid 52.7 Acetic anhydride 4.88 Component (gas phase HFO-1234yf product) 2,3,3,3-tetrafluoropropene 83.42 (HFO-1234yf)Tetrafluoroethene 0.75 1,1-difluoroethene 0.28 Trifluoroethene 1.692-chloro-1,1,1,2-tetrafluoroethane 11.62 (HCFC-124)

Example 3

Example 3 demonstrates the synthesis of2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) from CFC-114a inpyridine and the particular reaction products obtained from thissynthesis.

An 80 mL Fisher Porter tube was charged with 2.24 grams (0.034 mole) ofactivated zinc powder, 1.24 grams (0.041 mole) of paraformaldehyde and30 mL anhydrous pyridine under N₂. The tube was cooled to −15° C., and 5grams (0.029 mole) of 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a)were added and the reaction mixture was stirred at 50° C. for 8 hours.The reactor pressure dropped from 25 psig to 8 psig at the end of thereaction. The reaction mixture was cooled to room temperature andanalyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixturewas acidified with a 10% solution of HCl in acetone. The data isreported by area percent of GC-MS in Table 3.

TABLE 3 (liquid phase) GC-MS area Component percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 8.586 (CF₃CClFCH₂OH)2-chloro-1,1,1,2-tetrafluoroethane 2.887 (HCFC-124) Methyl formate 0.420Chlorotrifluoroethene (CFO-1113) 0.637 Trifluoroethene (HFO-1123) 0.0140Methanol 0.135 Pyridine 87.194

Example 4

Example 4 demonstrates the synthesis of2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) indimethylacetamide, and the particular reaction products obtained fromthis synthesis.

An 80 mL Fisher Porter tube was charged with 2.23 grams (0.034 mole) ofactivated zinc powder, 1.21 grams (0.040 mole) of paraformaldehyde and30 mL anhydrous dimethylacetamide under N₂. The tube was cooled to −15°C., and 5.2 grams (0.030 mole) of 1,1-dichloro-1,2,2,2-tetrafluoroethane(CFC-114a) were added. The reaction mixture was stirred at 60° C. for4.5 hours. The pressure of the reactor dropped from 30 psig to 9 psig atthe end of the reaction. The reaction mixture was cooled to roomtemperature, and it was analyzed by GC-MS. For GC-MS analysis, a portionof the reaction mixture was acidified with a 10% solution of HCl inacetone. The data is reported by area percent of GC-MS in Table 4.

TABLE 4 (liquid phase) GC-MS area Component percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 5.750 (CF₃CClFCH₂OH)2-chloro-1,1,1,2-tetrafluoroethane 2.181 (HCFC-124) Methyl formate 0.181Chlorotrifluoroethene (CFO-1113) 2.634 Trifluoroethene (HFO-1123) 0.029Dimethylacetamide 88.463

Example 5

Example 5 demonstrates the synthesis of CF₃CClFCH₂OZnCl in pyridine,with pre-treatment of formaldehyde, and the particular reaction productsobtained from this synthesis.

An 80 ml Fisher Porter tube was charged with 1.82 grams (0.06 mole) ofparaformaldehyde and 30 ml anhydrous pyridine under N₂. The tube washeated to 60° C. and stirred for 4 hours. The tube was cooled to roomtemperature, and 2.24 grams (0.034 mole) of activated zinc powder wereadded. After purging with N₂ for 15 minutes, the tube was cooled to −15°C. and 5 grams (0.029 mole) of 1,1-dichloro-1,2,2,2-tetrafluoroethane(CFC-114a) were added. Then the reaction mixture was stirred at 50° C.for 8 hours. The pressure of the reactor dropped from 25 psig to 9 psigat the end of the reaction. The reaction mixture was cooled to roomtemperature and analyzed by GC-MS. For GC-MS analysis, a portion of thereaction mixture was acidified with a 10% solution of HCl in acetone.The data is reported by area percent of GC-MS in Table 5. Theselectivity of 114a to CF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH)increased to 78.7%.

TABLE 5 (Liquid phase) GC-MS area Component percent (%)2-chloro-2,3,3,3-tetrafluoropropanol 12.06 (CF₃CClFCH₂OH), thatrepresents zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride(CF₃CClFCH₂OZnCl) 2-chloro-1,1,1,2-tetrafluoroethane 3.07 (HCFC-124)Methyl formate 1.02 Methanol 0.102 Trifluoroethene (HFO-1123) 0.18Pyridine 83.55

Example 6

Example 6 illustrates the esterification of2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH) with aceticanhydride to produce CF₃CClFCH₂OC(═O)CH₃ and the reaction productsobtained from this esterification.

An 80 ml Fisher Porter tube was charged with 2 grams (0.012 mole) ofCF₃CClFCH₂OH (which contains ˜15% diethyl ether), 1.35 grams (0.0132mole) of acetic anhydride and 0.25 grams of concentrated sulfuric acid.The mixture was stirred at 60° C. for 6 hours. The reaction mixture wascooled to room temperature and analyzed by GC-MS. The data is reportedby area percent of GC-MS in Table 6. These results show that more than99% of CF₃CClFCH₂OH has been converted to CF₃CClFCH₂OC(═O)CH₃.

TABLE 6 GC-MS area Component percent (%)2-chloro-2,3,3,3-tetrafluoropropyl acetate 72.55 (CF₃CClFCH₂OC(═O)CH₃)2-chloro-2,3,3,3-tetrafluoropropanol 0.198 (CF₃CClFCH₂OH) Ethyl acetate3.12 Acetic acid 17.24 Diethyl ether 6.19

Example 7

Example 7 illustrates the direct esterification of CF₃CClFCH₂OZnCl toCF₃CClFCH₂OC(═O)CH₃, and the reaction products obtained from this directesterification.

10 ml of a pyridine solution containing about 14% CF₃CClFCH₂OZnCl wasvacuum evaporated at room temperature to remove the majority of thepyridine. Then 2.0 grams acetic anhydride and 1 mL DMF were added to theresultant solid. The mixture was stirred at 60° C. for 7 hours. Thereaction mixture was cooled to room temperature and analyzed by GC-MS.The data is reported by area percent of GC-MS in Table 7.

TABLE 7 GC-MS area Component percent (%)2-chloro-2,3,3,3-tetrafluoropropyl acetate 71.8 (CF₃CClFCH₂OC(═O)CH₃)2-chloro-2,3,3,3-tetrafluoropropyl formate 2.01 (CF₃CClFCH₂OCH(═O))2-chloro-2,3,3,3-tetrafluoropropanol 0.115 (CF₃CClFCH₂OH) Aceticanhydride 2.61 Acetic acid 2.58 DMF/pyridine (solvent) 13.22

Example 8

Example 8 illustrates the conversion of2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃) to2,3,3,3-tetrafluoropropene (HFO-1234yf).

The reaction mixture from Example 7, above, was stirred with 1 gram ofNa₂CO₃ to remove the acid generated in the esterification step. Then 3moles of DMF and 1.3 grams of Zn were added. The reaction was run in an80 mL Fisher Porter tube at 50° C. for 2 hours and 60° C. for another 2hours with stirring. The pressure of the reactor increased from 0 psigto 13 psig. The reaction mixture was cooled to room temperature andanalyzed by GC-MS. The data is reported by area percent of GC-MS inTable 8. CF₃CClFCH₂OC(═O)CH₃ became non-detectable in the liquid phaseof the reactor. This result shows that CF₃CClFCH₂OC(═O)CH₃ has beenquantitatively converted to 2,3,3,3-tetrafluoropropene (HFO-1234yf)under the conditions above. Note that the vapor phase sample correspondsto the compositions comprising HFO-1234yf and additional compounds.

TABLE 8 GC-MS area Component (vapor phase) percent (%)2,3,3,3-tetrafluoropropene 94.48 (HFO-1234yf)2-chloro-2,3,3,3-tetrafluoropropanol 0.115 (CF₃CClFCH₂OH) Aceticanhydride 1.62 Methyl acetate 0.815 DMF 1.05 Pyridine 2.05 (Liquidphase) 2,3,3,3-tetrafluoropropene 1.61 (HFO-1234yf) Acetic anhydride1.45 Methyl acetate 0.61 DMF 86.24 Pyridine 9.98

Example 9

Example 9 demonstrates the reaction of1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a) with paraformaldehydeto form zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride(CF₃CClFCH₂OZnCl) in a mixed solvent of dimethylformamide and pyridine.

An 80 mL Fisher Porter tube was charged with 2.2 grams Zn (0.037 mole),0.3 grams zinc acetate (0.0016 mole), 2 grams (0.067 mole) ofparaformaldehyde, 15 grams of anhydrous pyridine and 15 grams ofdimethylformamide under N₂. After N₂ purge for 15 min, the tube wascooled to −15° C. and 5 grams (0.029 mole) of1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a) was added and thereaction mixture was stirred at 50° C. for 2 hours. The pressure of thereactor dropped from 25 psig to 5 psig at the end of the reaction. Thereaction mixture cooled to room temperature and analyzed by GC-MS. ForGC-MS analysis, a portion of the reaction mixture was acidified with a10% solution of HCl in acetone. The data is reported by area percentfrom GC-MS in Table 9 (DMF and pyridine peaks are excluded from theintegration, i.e., are present in the sample). The selectivity ofCFC-114a to CF₃CClFCH₂OZnCl (analyzed as 2,3,3,3-tetrafluoropropanol(CF₃CClFCH₂OH)) was 83% based on GC-MS analysis.

TABLE 9 (Liquid phase) GC-MS Component area percent Tetrafluoroethene(TFE) 0.18 Acetic Acid 3.1 Methyl formate 0.24 Methyl acetate 0.682-chloro-1,1,1,2-tetrafluoro ethane 5.18 (HCFC-124)2,3,3,3-tetrafluoropropene 4.61 (HFO-1234yf) 2,3,3,3-tetrafluoropropanol80.1 (CF₃CClFCH₂OH), that represents zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl)2-chloro-2,3,3,3-tetrafluoropropyl 3.744 acetate (CF₃CClFCH₂OC(═O)CH₃)

Example 10

Example 10 illustrates esterification of CF₃CClFCH₂OZnCl directly toCF₃CClFCH₂OC(═O)CH₃ with acetic anhydride in a solvent mixture, and thereaction products obtained from this esterification.°

Excess Zn was filtered from the reaction mixture obtained in Example 9,then the filtrate was charged to an 80 mL Fisher Porter tube, and 4.4grams of acetic anhydride (0.043 mole) were added. The mixture wasstirred at 60° C. for 6 hours. The reaction mixture cooled to roomtemperature and was analyzed by GC-MS. The data is reported by areapercent of GC-MS in Table 10 (DMF, pyridine and acetic anhydride wereexcluded from integration), i.e., they were present in the finalcomposition. This result shows that more than 94% of CF₃CClFCH₂OZnCl hasbeen converted to CF₃CClFCH₂OC(═O)CH₃ at these reaction conditions.

TABLE 10 (Liquid phase) GC-MS Component area percent TFE 0.4772-chloro-1,1,1,2-tetrafluoro ethane 5.97 (HCFC-124)3-chloro-3,4,4,4-trifluoro-2-butanone 2.57 (CF₃CClFCH₂C(═O)CH₃) Ethylmethyl ether 0.83 Methyl acetate 0.92 2-chloro-2,3,3,3-tetrafluoropropylacetate 85.3 (CF₃CClFCH₂OC(═O)CH₃) Unknowns 2.46

Example 11

Example 11 illustrates the synthesis of 2,3,3,3-tetrafluoropropene(HFO-1234yf) from 1,1,1,2-tetrafluoro-2,2-dichloroethane (CFC-114a) in3:1 pyridine:DMF solvent.

An 80 mL Fisher Porter tube was charged with 2.1 grams zinc metal (0.032mole), 0.3 grams zinc acetate (0.0016 mole), 2 grams (0.067 moles) ofparaformaldehyde, 30 grams anhydrous pyridine under N₂. After N₂ purgefor 15 minutes, the tube was cooled to −15° C. and 5 grams (0.029 moles)of 1,1-dichlorotetrafluoroethane (CFC-114a) were added. Then thereaction mixture was stirred at 50° C. for 3 hours. The pressure of thereactor dropped from 25 psig to 5.5 psig at the end of the reaction.After the reaction mixture cooled to room temperature, it was analyzedby GC-MS. For GC-MS analysis, a portion of the reaction mixture wasacidified with a 10% solution of HCl in acetone. The solvent (pyridine)peak was excluded from the integration. The data is reported in Table 11by area percent of GC-MS. The selectivity of1,1-dichlorotetrafluoroethane to CF₃CClFCH₂OZnCl (analyzed asCF₃CClFCH₂OH) is 81% based on GC-MS analysis.

The excess zinc was filtered off from the reaction mixture and it wascharged to an 80 mL Fisher Porter tube. 10 mL of anhydrous DMF and 3.5grams of acetic anhydride (0.034 moles) were also added to the reactor.The mixture was stirred at 60° C. for 4 hours. The reaction mixture wascooled to room temperature and analyzed by GC-MS. The data is reportedin Table 12 by area percent of GC-MS. The solvent (DMF and pyridine)peak were excluded from the integration. This result shows that morethan 98% of CF₃CClFCH₂OZnCl has been converted, and selectivity toCF₃CClFCH₂OC(═O)CH₃ and CF₃CFClCH₂OCH₂C(═O)CH₃ are 89%.

10 mL of the reaction mixture above was left in an 80 mL Fisher Portertube and activated zinc powder (1 gram, 0.015 moles) was added. Thereaction was run at 60° C. for 4 hours with stirring. The pressure ofthe reactor increased from 6 psig to 15.5 psig. The reaction mixture wascooled to room temperature and the vapor phase and liquid phase wereanalyzed by GC-MS. The data is reported by area percent of GC-MS. Thevapor phase (product 2,3,3,3-tetrafluoropropene) data is listed in Table13 and the liquid phase (remaining after reaction) data is listed inTable 14 (the solvent peaks for DMF and pyridine were excluded from theintegration). CF₃CClFCH₂OC(═O)CH₃ became non-detectable in the liquidphase of the reactor. Analysis shows that selectivity to2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) was about 94%, andselectivity to 1,3-bis-trifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈)was about 5%.

TABLE 11 Liquid phase CF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH) GC-MSCompounds area % Trifluoroethylene (HFO-1123) 1.93 Trifluoroacetaldehyde1.05 Formaldehyde 0.633 2-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124)12.77 1,1-Dichloro-1,2,2,2-tetrafluoroethane (CFC- 0.378 114a) Methanol0.275 Methyl formate 0.14 2-chloro-2,3,3,3-tetrafluoropropanol 74.68(CF₃CClFCH₂OH), that represents zinc (2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl)2-chloro-2,3,3,3-tetrafluoropropyl acetate 1.648 (CF₃CClFCH₂OC(═O)CH₃)Unknowns 6.39

TABLE 12 Liquid phase 2-chloro-2,3,3,3-tetrafluoropropanol GC-MSCompounds area % Trifluoroethylene (HFO-1123) 0.682,3,3,3-tetrafluoropropene (HFO1234yf) 0.04 Water 2.45 Formaldehyde 0.132-Chloro-1,1,1,2-tetrafluoro ethane (HCFC-124) 8.741,1-Dichloro-1,2,2,2-tetrafluoroethane (CFC- 1.03 114a) Methyl acetate0.69 Methyl formate 0.17 3-chloro-3,4,4,4-tetrafluoro-2-butanone 1.4452,3,3,3-tetrafluoropropyl acetate 0.312-chloro-2,3,3,3-tetrafluoropropanol 1.67 (CF₃CClFCH₂OH)2-chloro-2,3,3,3-tetrafluoropropyl acetate 65.39 (CF₃CClFCH₂OC(═O)CH₃)Acetic anhydride 3.33 2-chloro-2,3,3,3-tetrafluoropropoxy methyl 6.47acetate (CF₃CFClCH₂OCH₂OC(═O)CH₃) Unknowns 7.42

TABLE 13 Vapor phase product (2,3,3,3-tetrafluoropropene) GC-MSCompounds area % Tetrafluoroethylene (TFE) 0.08 Trifluoroethylene(HFO-1123) 5.84 1,1,1-trifluoroethane 0.02 2,3,3,3-tetrafluoropropene(HFO-1234yf) 79.93 Chlorotrifluoroethylene (CFO-1113) 0.062-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124) 9.101,1-dichloro-1,2,2,2-tetrafluoroethane 0.051,3-bis-trifluoromethyl-1,3-difluorocyclobutane 4.00 (C₆H₄F₈) Methylformate 0.04 Acetic acid 0.19 2,3,3,3-tetrafluoropropyl acetate 0.1Unknowns 0.85

TABLE 14 Liquid phase (remaining after reaction) GC-MS Compounds area %Trifluoroethylene (HFO-1123) 0.98 1,1,1-Trifluoroethane (HFC-143a) 0.492,3,3,3-tetrafluoropropene (HFO-1234yf) 36.85 Water 8.26 Methanol 0.25Acetic acid 3.47 2-Chloro-1,1,1,2-tetrafluoro ethane (HCFC-124) 20.45Methyl acetate 2.10 Methyl formate 0.321,3-bis-trifluoromethyl-1,3-difluorocyclobutane 7.91 (C₆H₄F₈)2,3,3-trifluoro-2-propen-1-ol acetate 2.02 2,3,3,3-tetrafluoropropylacetate 2.92 Methyl ethyl ether 1.462 Acetic anhydride 7.245 Unknowns5.27

Example 12

Example 12 illustrates the synthesis of 2,3,3,3-tetrafluoropropene(HFO-1234yf) from 1,1,1,2-tetrafluoro-2,2-dichloroethane (CFC-114a) in1:1 pyridine:DMF solvent.

A 80 mL Fisher Porter tube was charged with 2.1 grams of zinc metal(0.032 moles), 0.3 grams zinc acetate (0.0016 moles), 2 grams (0.067moles) of paraformaldehyde, 0.2 grams of bis(hydrogenated alkyl)dimethyl ammonium acetate and 30 grams of anhydrous pyridine under N₂.After N₂ purge for 15 minutes, the tube was cooled to −15° C. and 5grams (0.029 moles) of 1,1-dichlorotetrafluoroethane (CFC-114a) wereadded. Then the reaction mixture was stirred at 50° C. for 3 hours. Thepressure of the reactor dropped from 23 psig to 5.5 psig at the end ofthe reaction. The reaction mixture cooled to room temperature andanalyzed by GC-MS. For GC-MS analysis, a portion of the reaction mixturewas acidified with a 10% solution of HCl in acetone. The solvent for DMFand pyridine were excluded from the integration. The data is reported inTable 15 as area percent from GC-MS data. The selectivity for CFC-114ato CF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH) was about 85% based onGC-MS analysis.

10 mL of the reaction mixture was filtered and charged into an 80 mLFisher Porter tube. 10 mL of anhydrous DMF and 3.5 grams of aceticanhydride (0.034 moles) were also added to the reactor. The mixture wasstirred at 60° C. for 4 hours. The reaction mixture was cooled to roomtemperature and analyzed by GC-MS. The data is reported in Table 16 asarea percent from GC-MS data. The solvent peaks for DMF and pyridinewere excluded from the integration. This result shows that more than 98%of CF₃CClFCH₂OZnCl was converted, and selectivity forCF₃CClFCH₂OC(═O)CH₃ and CF₃CFClCH₂OCH₂C(═O)CH₃ are about 95%.

The reaction mix above was treated with 2 grams of Na₂CO₃ in an 80 mLFisher Porter tube. After Na₂CO₃ was filtered off, activated zinc powder(1 gram, 0.015 moles) was added. The reaction was run in 80 mL FisherPorter tube at 60° C. for 4 hour with stirring. The pressure of thereactor increased from 5 psig to 18 psig. The reaction mixture wascooled to room temperature and the liquid and vapor phases were analyzedby GC-MS. The data is reported by area percent of GC-MS. The results forthe vapor phase (product 2,3,3,3-tetrafluoropropene) are listed in Table17 and the results for the liquid phase (remaining after reaction) arereported in Table 18 (solvent peaks for DMF and pyridine were excludedfrom the integration). More than 99% CF₃CClFCH₂OC(═O)CH₃ and more than95% CF₃CFClCH₂OCH₂C(═O)CH₃ were converted. Analysis shows thatselectivity for HFO-1234yf was about 98%, and selectivity for1,3-bis-trifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈) was about 0.1%.

TABLE 15 Liquid phase CF₃CClFCH₂OZnCl (analyzed as CF₃CClFCH₂OH) GC-MSCompounds area % Trifluoroethylene (HFO-1123) 1.06 Trifluoroacetaldehyde0.09 2,3,3,3-tetrafluoropropene (HFO-1234yf) 0.03 Formaldehyde 0.852-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124) 8.331,1-Dichloro-1,2,2,2-tetrafluoroethane (CFC- 1.55 114a) Dimethyl ether0.14 Methyl formate 0.55 Ethyl formate 0.202-chloro-2,3,3,3-tetrafluoropropanol 85.70 (CF₃CClFCH₂OH), thatrepresents zinc (2- chloro-2,3,3,3-tetrafluoropropoxy) chloride(CF₃CClFCH₂OZnCl) 2-chloro-2,3,3,3-tetrafluoropropyl acetate 0.285(CF₃CClFCH₂OC(═O)CH₃) Acetic anhydride 0.10 Unknowns 0.656

TABLE 16 Liquid phase 2-chloro-2,3,3,3-tetrafluoropropyl acetate GC-MSCompounds area % 2-Chloro-1,1,1,2-tetrafluoro ethane (HCFC- 3.17 124)1,1-Dichloro-1,2,2,2-tetrafluoroethane (CFC- 0.62 114a) Methyl acetate0.72 Ethyl formate 0.10 Methyl formate 0.43 Acetic acid 15.063-chloro-3,4,4,4-tetrafluoro-2-butanone 0.322-chloro-2,3,3,3-tetrafluoropropanol 1.74 (CF₃CClFCH₂OH)2-chloro-2,3,3,3-tetrafluoropropyl acetate 68.00 (CF₃CClFCH₂OC(═O)CH₃)Acetic anhydride 0.886 2-chloro-2,3,3,3-tetrafluoropropoxy methyl 7.63acetate (CF₃CFClCH₂OCH₂OC(═O)CH₃) Unknowns 1.32

TABLE 17 Vapor phase product (2,3,3,3-tetrafluoropropene) GC-MSCompounds area % Trifluoroethylene (HFO-1123) 0.722,3,3,3-tetrafluoropropene (HFO-1234yf) 97.46 Water 0.04Chlorotrifluoroethylene (CFO-1113) 0.061,3-bis-trifluoromethyl-1,3-difluorocyclobutane 0.1 (C₆H₄F₈) Methylformate 0.08 Methyl acetate 0.1 Unknowns 0.1

TABLE 18 Liquid phase remaining after reaction GC-MS Compounds area %Trifluoroethane (HFO-1123) 0.03 2,3,3,3-tetrafluoropropene (HFO-1234yf)35.26 Water 0.20 Ethyl formate 0.26 Ethyl acetate 0.24 Acetic acid 11.732-Chloro-1,1,1,2-tetrafluoroethane (HCFC-124) 5.89 Methyl acetate 2.10Methyl formate 1.0 1,3-bis-trifluoromethyl-1,3-difluorocyclobutane 0.25(C₆H₄F₈) 2-chloro-2,3,3,3-tetrafluoropropanol 0.22 (CF₃CClFCH₂OH)2,3,3-trifluoro-2-propen-1-ol acetate 1.042-chloro-2,3,3,3-tetrafluoropropyl acetate 0.70 (CF₃CClFCH₂OC(═O)CH₃)2,3,3,3-tetrafluoropropyl acetate 0.422-chloro-2,3,3,3-tetrafluoropropoxy methyl 2.27 acetate(CF₃CFClCH₂OCH₂OC(═O)CH₃) Acetic anhydride 12.4 Pyridinyl ethanone 15.58Dimethylacetamide 3.00 Unknowns 7.49

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges, include each and everyvalue within that range.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

What is claimed is:
 1. A composition comprising HFO-1234yf and at leastone additional compound selected from the group consisting of CFC-114a(2-dichloro-1,1,1,2-tetrafluoroethane, CCl₂FCF₃), HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHFCl), HFC-143a(1,1,1-trifluoroethane, CF₃H₃), CFO-1113(2-chloro-1,1,2-trifluoroethene, CClF═CF₂), HFO-1123(1,1,2-trifluoroethene, CHF═CF₂), HFO-1132a (1,1-difluoroethene,CH₂═CF₂), TFE (tetrafluoroethene, CF₂═CF₂), HCFO-1122(2-chloro-1,1-difluoroethene, CHCl═CF₂), 3,4,4,4-tetrafluoro-2-butanone(CH₃C(═O)CHFCF₃), acetyl fluoride (CH₃C(═O)F),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH),2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃), Zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl),2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate(CF₃CFClCH₂OCH₂C(═O)CH₃), 1,3-bistrifluoromethyl-1,3-difluorocyclobutane(C₆H₄F₈), 2,3,3,3-tetrafluoropropyl acetate (CF₃CHFCH₂C(═O)CH₃),dimethylformamide (DMF, HCON(CH₃)₂), pyridine (C₅H₅N), ethyl acetate,(CHClFCF₃), acetic acid (CH₃C(═O)OH), diethyl ether (CH₃CH₂OCH₂CH₃),acetic anhydride (CH₃C(═O)OC(═O)CH₃), methyl acetate (CH₃C(═O)OCH₃),dimethylacetamide (CH₃C(═O)N(CH₃)₂), methanol (CH₃OH), ethanolCH3CH2OH), methyl formate (HC(═O)OCH₃), pyrazine, pyrimidine,N-methylpyrrolidine, N-methylpiperidine, hexamethylphosphoramide,tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidinone, dimethyl sulfoxide,acetonitrile, benzonitrile, and mixtures thereof; provided that thecomposition comprises HFC-143a, HFO-1123, CFO-1113, HCFC-124 andCFC-114a.
 2. The composition of claim 1, wherein the additionalcompounds comprise methyl formate, acetic acid and2,3,3,3-tetrafluoropropyl acetate.
 3. The composition of claim 1,wherein the additional compounds comprise TFE, HFO-1123, HFC-143a,CFO-1113, HCFC-124, CFC-114a,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, aceticacid, and 2,3,3,3-tetrafluoropropyl acetate.
 4. The composition of claim1, wherein the additional compounds comprise HFO-1123, water, CFO-1113,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, andmethyl acetate.
 5. The composition of claim 1 wherein the composition isin the vapor phase, and the total amount of said compounds other thanHFO-1234yf is about 30 weight percent, or less.
 6. The composition ofclaim 5 wherein the composition contains less than 10 ppm HFO-1234ze. 7.A composition comprising: a. at least one compound selected fromCF₃CClFCH₂OH, CF₃CClFCH₂OC(═O)CH₃ and CF₃CClFCH₂OZnCl; b. at least onesolvent; c. HFO-1234yf; d. CFO-1113 e. HCFC-124; f. HFO-1123; and g.CFC-114a.
 8. The composition of claim 7 comprising CF₃CClFCH₂OH andfurther comprising at least one additional compound selected from thegroup consisting of HFO-1132a, TFE, HCFO-1122, dimethylacetamide,methanol, methyl acetate, methyl formate, DMF, pyridine, ethyl acetate,acetic acid, diethyl ether, CF₃CClFCH₂OZnCl, CF₃CClFCH₂OC(═O)CH₃,2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate, and mixturesthereof.
 9. The composition of claim 7 comprising CF₃CClFCH₂OC(═O)CH₃and further comprising at least one additional compound selected fromthe group consisting of HFO-1132a, TFE, HCFO-1122, methanol, methylacetate, methyl formate, dimethylacetamide, dimethylformamide, pyridine,ethyl acetate, acetic acid, diethyl ether, acetic anhydride,formaldehyde, 3-chloro-3,4,4,4-trifluoro-2-butanone,2,3,3,3-tetrafluoropropyl acetate, CF₃CClFCH₂OCH(═O),2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate, CF₃CClFCH₂OH,CF₃CClFCH₂OZnCl, and mixtures thereof.
 10. The composition of claim 7comprising CF₃CClFCH₂OZnCl and further comprising at least oneadditional compound selected from the group consisting of HFO-1132a,TFE, HCFO-1122, methanol, methyl acetate, methyl formate,dimethylacetamide, dimethylformamide, pyridine, ethyl acetate, aceticacid, diethyl ether, formaldehyde, trifluoroacetaldehyde, CF₃CClFCH₂OH,CF₃CClFCH₂C(═O)CH₃, 2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate(CF₃CFClCH₂OCH₂OC(═O)CH₃), and mixtures thereof.
 11. The compositionclaim 7, 8, 9 or 10 comprising methyl formate and acetic acid.
 12. Thecomposition of claim 9 comprising methyl formate, acetic acid and2,3,3,3-tetrafluoropropyl acetate.
 13. The composition of claim 7wherein said solvent is selected from the group consisting of alkyl,dialkyl, or trialkyl linear or cylic amines; pyridine oralkyl-substituted pyridines, pyrazine, pyrimidine; sulfoxides, ethers,alkyl or aromatic nitriles, hexamethylphosphoramide; alcohols; esters,dimethylformamide, tetrahydrofuran, dimethylacetamide, 1,4-dioxane, andN-methylpyrrolidone, and mixtures thereof.
 14. The composition of claim13 wherein said solvent is selected from the group consisting ofmethanol, ethanol, methyl formate, DMSO, acetonitrile, benzonitrile, andmixtures thereof.
 15. The composition of claim 13 wherein said solventis selected from the group consisting of dimethylacetamide,dimethylformamide, pyridine, and mixtures thereof.
 16. A compositioncomprising HFO-1234yf and at least one additional compound selected fromthe group consisting of CFC-114a (2-dichloro-1,1,1,2-tetrafluoroethane,CCl₂FCF₃), HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHFCl),HFC-143a (1,1,1-trifluoroethane, CF₃CH₃), CFO-1113(2-chloro-1,1,2-trifluoroethene, CClF═CF₂), HFO-1123(1,1,2-trifluoroethene, CHF═CF₂), HFO-1132a (1,1-difluoroethene,CH₂═CF₂), TFE (tetrafluoroethene, CF₂═CF₂), HCFO-1122(2-chloro-1,1-difluoroethene, CHCl═CF₂), 3,4,4,4-tetrafluoro-2-butanone(CH₃C(═O)CHFCF₃), acetyl fluoride (CH₃C(═O)F),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH),2-chloro-2,3,3,3-tetrafluoropropyl acetate (CH₃CClFCH₂OC(═O)CH₃), Zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl),2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate(CF₃CFClCH₂OCH₂OC(═O)CH₃),1,3-bistrifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈),2,3,3,3-tetrafluoropropyl acetate (CF₃CHFCH₂OC(═O)CH₃),dimethylformamide (DMF, HCON(CH₃)₂), pyridine (C₅H₅N), ethyl acetate,(CHClFCF₃), acetic acid (CH₃C(═O)OH), diethyl ether (CH₃CH₂OCH₂CH₃),acetic anhydride (CH₃C(═O)OC(═O)CH₃), methyl acetate (CH₃C(═O)OCH₃),dimethylacetamide (CH₃C(═O)N(CH₃)₂), methanol (CH₃OH), ethanolCH3CH2OH), methyl formate (HC(═O)OCH₃), pyrazine, pyrimidine,N-methylpyrrolidine, N-methylpiperidine, hexamethylphosphoramide,tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidinone, dimethyl sulfoxide,acetonitrile, benzonitrile, and mixtures thereof; provided that thecomposition comprises CFO-1113; and that the composition containsgreater than zero weight percent to less than 1 weight percent of the atleast one additional compound.
 17. The composition of claim 16comprising HCFO-1122 (2-chloro-1,1-difluoroethene, CHCl═CF₂).
 18. Thecomposition of claim 17 comprising HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHFCl).
 19. The composition ofclaim 16 comprising HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane,CF₃CHFCl).
 20. The composition of claim 19 wherein the additionalcompounds comprise TFE, HFO-1123, HFC-143a, HCFC-124, CFC-114a,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, aceticacid, and 2,3,3,3-tetrafluoropropyl acetate.
 21. The composition ofclaim 19 wherein the additional compounds comprise HFO-1123, water,1,3-bis-trifluoromethyl-1,3-difluorocyclobutane, methyl formate, andmethyl acetate.
 22. A composition comprising HFO-1234yf and at least oneadditional compound selected from the group consisting of CFC-114a(2-dichloro-1,1,1,2-tetrafluoroethane, CCl₂FCF₃), HCFC-124(2-chloro-1,1,1,2-tetrafluoroethane, CF₃CHFCl), HFC-143a(1,1,1-trifluoroethane, CF₃CH₃), CFO-1113(2-chloro-1,1,2-trifluoroethene, CClF═CF₂), HFO-1123(1,1,2-trifluoroethene, CHF═CF₂), HFO-1132a (1,1-difluoroethene,CH═CF₂), TFE (tetrafluoroethene, CF₂═CF₂), HCFO-1122(2-chloro-1,1-difluoroethene, CHCl═CF₂), 3,4,4,4-tetrafluoro-2-butanone(CH₃C(═O)CHFCF₃), acetyl fluoride (CH₃C(═O)F),2-chloro-2,3,3,3-tetrafluoropropanol (CF₃CClFCH₂OH),2-chloro-2,3,3,3-tetrafluoropropyl acetate (CF₃CClFCH₂OC(═O)CH₃), Zinc(2-chloro-2,3,3,3-tetrafluoropropoxy) chloride (CF₃CClFCH₂OZnCl),2-chloro-2,3,3,3-tetrafluoropropoxy methyl acetate(CF₃CFClCH₂OCH₂OC(═O)CH₃),1,3-bistrifluoromethyl-1,3-difluorocyclobutane (C₆H₄F₈),2,3,3,3-tetrafluoropropyl acetate (CF₃CHFCH₂OC(═O)CH₃),dimethylformamide (DMF, HCON(CH₃)₂), pyridine(C₅H₅N), ethyl acetate,(CHClFCF₃), acetic acid (CH₃C(═O)OH, diethyl ether (CH₃CH₂OCH₂CH₃),acetic anhydride (CH₃C(═O)OC(═O)CH₃), methyl acetate (CH₃C(═O)OCH₃),dimethylacetamide (CH₃C(═O)N(CH₃)₂), methanol (CH₃OH), ethanolCH3CH2OH), methyl formate (HC(═O)OCH₃), pyrazine, pyrimidine,N-methylpyrrolidine, N-methylpiperidine, hexamethylphosphoramide,tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidinone, dimethyl sulfoxide,acetonitrile, benzonitrile, and mixtures thereof; provided that theadditional compounds comprise CFO-1113, tetrafluoroethene,1,1,difluoroethene, trifluoroethene and2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124).